Chromhjm-containing azo dyestuffs



United States Patent 6) 1 3,169,951 CHROMIUM-CONTAINING AZO DYFSTUFFS Arthur Buehler, Rheinfelden, Aargau, Switzerland, and

Gerhard Back, Lorrach, Baden, Germany, assignors to Ciba Limited, Basel, Switzerland, a company of Switzerland N Drawing. Filed Oct. 7, 1963, Ser. No. 314,522 Claims priority, application Switzerland, Oct. 10, 1962, 11,875/62; Sept; 4; 1963; 10,927/63 9 Claims. (Cl. 260-145) The present invention is based on the observation that valuable new chromium-containing azo dyestufls that contain one atom of chromium bound in complex union with two molecules of different monoazo dyestuffs are obtained when a monoazo dyestuit of the formula on no z X X in which one X represents a sulphonic acid group and the other two Xs represent hydrogen atoms, Y represents a hydrogen atom or a nitrogroup, and Z represents a hydrogen atom or a chlorine atom or a nitro group or a lowmolecular alkyl or alkoxy group, and in which Y and Z must be different from each other. I

The monoazo dyestuffs of the Formula 1 used in the present process can be prepared in known manner by coupling -chloroor 5:8 dichloro-1-hydroxynaphthalene with orthohydroxy-diazo compounds prepared from amines of the formula in which Y, Z and R have the meanings ascribed to them in Formula 1, in a weakly acid to alkaline medium.

As examples of such amines there may be mentioned 2-amino-1-hydroxybenzene 4-methylor 4-methoxy-2-arnino-l-hydroxybenzene, S-chloro-Z-amino-l-hydroxybenzene, 4:6-dichloro-2-amino-l-hydroxybenzene,

3 :4: 6-trichloro-2-amino-l-hydroxybenzene, 4-chloro-5- or -6-nitro-2-amino-l-hydroxybenzene, 6-nitro-4-methyl-2-amino-l-hydroxybenzene,

2 5-chloro-4-methoxy-2-amino-l hydroxybenzene, 4 nitro-6-chloro-2-amino-1-hydroxybenzene,

4: 6-dinitro-2-amino-1-hydroxybenzene, especially 4- or S-nitro-Z-amino-l-hydroxybenzene, and 4-chloro-2-amino-l-hydroxybenzene.

The monoazo dyestuffs of the Formula 2 can likewise be prepared in known manner by coupling l-hydroxynaphthalene-3-, -4- or -5-sulphonic acid with diazo compounds prepared, for example, from 4-chloro, 4-methyl-, 4-methoxyor 4-nitro-2aminophenol, 5-nitro-2-aminophenol or 4-chloro-, 4-rnethylor 4-methoxy-5-nitro- Z-aminophenol. Their conversion into 1:1 chromium complexes may be performed by conventional known methods, for example, by reacting them in an acid medium at boiling temperature or, if necessary, at a temperature above C. with an excess of a salt of trivalent chromium, for example, chromium formate, chromium sulphate or chromium fluoride. It is generally of advantage to carry out the metallisation in known manner in an aqueous medium, if necessary, in the presence of an organic solvent, for example, alcohol or formamide.

As is known, the 1:1 metal complexes of ortho-ortho'- dihydroxy-monoazo dyestuffs can be prepared not only from the ortho:ortho-dihydroxy-monoazo dyestuffs themselves, but also from the corresponding ortho-alkoxyortho'-hydroxy-monoazo dyestufls. Accordingly, for the preparation of the chromium-containing dyestuffs used as starting materials in the present process there can be used, instead of the ortho-hydroxydiazo compound of the Formula 2, the corresponding ortho-alkoxydiazo compound, especially the methoxy compound.

In the present process it isgenerally of advantage not to dry the starting dyestufits after their preparation and precipitation, but to use them in the form of a moist paste for further processing.

The reaction of the 1:1 chromium complexes with the metal-free dyestuiis is advantageously carried out in a neutral to slightly alkaline aqueous medium in an open or closed vessel at room temperature or at an elevated temperature, for example, at a temperature between 50 and C. The addition of solvents, for example, alcohol or formamide, can assist the reaction in some cases.'

It is generally of advantage to react equivalent proportions of chromium-containing 1:1 complexes and metalfree dyestuffs, the molar ratio between metal-free dyestuffs and 1:1 complex advantageously being at least 0.85:1 and 1:0.85; an excess of metal-containing dyestuflf is generally less disadvantageous than an excess of metal-free dyestufi. The closerthis ratio is to 1:1, the more advantageous is the result.

The new chromium-containing mixed complexes obtainable by the present process are suitable for dyeing and printing a very wide variety of materials, but more especially for dyeing animal materials, for example, silk, leather and more especially wool. They are also suitable for dyeing and printing synthetic fibers made from polyamides, polyurethanes and polyacrylonitrile, and also fibre mixtures, for example, wool/polyamide mixtures. They are mainly suitable for application from weakly alkaline, neutral or weakly acid bath, for example, an acetic acid bath. The dyeings so obtained are uniform and possess a good fastness to light, to washing, to milling, to decatising and to carbonising. They are also distinguished by their favourable appearance in artificial light.

The following example illustrates the invention. Unless otherwise stated, the parts and percentages are by weight.

' E ampl 44.1 partstof the 1:1 chromium ooinplex of a dyestulf prepared from diazotised 5-nitro-2-amino-l-hydroxybenzene and 1hydroXynaphtahalene-5-sulphonic acid and 36.75 parts of a dyestuff prepared irom diazotised 4-ichlo- 5 r0 2 :amino-l-hydroxybenzene and 5 :8-dichloro-1-hydroxynaphthalene are stirred in 5000 partsof hot Water and the mixture is then neutralisedi 6.0 parts of sodium hydroxide are added, and the mixture is'stirred at 95* to 98 C. until both starting dyestuffs have practically dis; 10'

appeared. The dyestulf i then precipitated out ofthe resulting blue-black solution by the addition of sodium ch1'oride, filtered off and dried. It constitutes a blue-black powder that dissolves in water to give a blue solution and in column II are reacted with the 1:1 chromium complex v compounds of the corresponding monoazo dyestuffs listed in column I in a molar ratio of 1'::l. Column III indicates the tints obtained on wool Withthe dyestuffs listed.

r 1r q m 9H OH N=N- Dark blue.

()H OH N= N=N-' D0.

SOzH 1 1 OH OH N=N Do.

OH OH OH OnN I t 505E 11 V V on I on 0H N=N' N=N- Rcddish blue.

. I V OCH; 803B 7 V 1 11 on 7 OH I on HO o1 N=N- N=N Blue.

om S0311 1 ()H OH OQN Q OH on:

I II III OH OH OH (I)H N=N N=N Blue violet.

OzN

CH on on no or N: O N N= Blue-grey.

onv on N==N Grey.-

OQN

S O R OH OH N=N- Dark blue.

OgN 7 OH OH N=N Blue.-

0,N HO3S- OH OH OH H0 01 om N=N' N= Reddlshv blue.

l 80:11 1 (El OH OH OH B0 C1 O N N=N- DO.

OH OH X i N=N'[ I 1 Rx x and

whereinY and Z each represent a member selected from 75 the group consisting of hydrogemchlorine and nit-no, R is a member selected from the group consisting of hydrogen, chlorine, nitro, at most Y and R representing simultaneously nitro, Xis a member selected from the group 0onsisting of hydrogen and chlorine, R is a member selected fromthe group consisting of hydrogen and nitro, R is a member selected from the group consisting of hydrogen, chlorine, nitro, methyl and methoxy, R and R being different from each other, and one X is sulfonic acid and the other two Xfs hydrogen.

2. A complex chromium compound containing one atom of chromium incomplex'union with two monoazodyestufi molecules of the formulae 500 OzNl 5 X1 X1 wherein one X is sulfonic acid and the other X is hydrohydrogen, one Y is nitro and the other Y is hydrogen. 3. The complex chromium compound containing one atom of chromium in complex union with two monoazodyestuff molecules of the formulae OH OH $1 and and

4. The complex chromium compound containing one atom of chromium in complex union with two monoazodyestuif molecules of the formulae OH Cl and 5. The complex chromium compound containing one atom of chromium in complex union with two monoazodyestuff molecules of the formulae SOaH OH Cl and 6. The complex chromium compound containing one atom of chromium in complex union with two monoazodyestuff molecules of the formulae 7. The complex chromium compound containing one atom of chromium in complex union with two monoazodyestuff molecules of the formulae OH Cl 8. The complex chromium compound containing one atom of chromium in complex union with two monoazodyestutf molecules of the formulae 9. The complex chromium compound containing one atom of chromium in complex union with two monoazodyestulf molecules of the formulae and and

and

and

No references cited.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 ,169 ,951 February 16 1965 Arthur Buehler et al.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 9, lines 45 to 52, the left-hand portion of the formula should appear as shown below insted of as in the patent:

Signed and sealed this 27th day of July 1965. (SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Attcsting Officer Commissioner of Patents 

1. A COMPLEX CHROMIUM COMPOUND CONTAINING ONE ATOM OF CHROMIUIM IN COMPLEX UNION WITH TWO MONOAZODYESTUFF MOLECULES OF THE FORMULAE 